CN105592923B - The hydrotreating method of the hydrotreating catalyst of heavy hydrocarbon oil, the manufacture method of the hydrotreating catalyst of heavy hydrocarbon oil and heavy hydrocarbon oil - Google Patents
The hydrotreating method of the hydrotreating catalyst of heavy hydrocarbon oil, the manufacture method of the hydrotreating catalyst of heavy hydrocarbon oil and heavy hydrocarbon oil Download PDFInfo
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- CN105592923B CN105592923B CN201480052589.8A CN201480052589A CN105592923B CN 105592923 B CN105592923 B CN 105592923B CN 201480052589 A CN201480052589 A CN 201480052589A CN 105592923 B CN105592923 B CN 105592923B
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- zinc
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- hydrotreating
- metal
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1808—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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Abstract
It is an object of the present invention to provide can improve the method for the storage-stable of the heavy hydrocarbon oil after hydrotreating without making hydrotreating catalyst that desulphurizing activated and metal removal activity reduces and carrying out hydrotreating to heavy hydrocarbon oil using the hydrotreating catalyst；The present invention provides a kind of hydrotreating catalyst of heavy hydrocarbon oil, it is characterized in that, contain the aluminium oxide of phosphorous/zinc as carrier, the alumina support of the phosphorous/zinc by the phosphorus of 0.1~4 mass % on the basis of carrier and based on oxide conversion and the zinc oxide particles containing based on the basis of carrier 1~12 mass %；Supported on above-mentioned carrier by the basis of catalyst and based on oxide conversion 8~20 mass % selected from least one of the 6th race's metal of periodic table and by the basis of catalyst and based on oxide conversion 2~6 mass % selected from least one of the 8th~10 race's metal of periodic table；Wherein, the average grain diameter of above-mentioned zinc oxide particles is 2~12 μm.
Description
Technical field
The present invention relates to for the air-distillation residue oil (hereinafter also referred to as " AR ") by direct desulfurization unit or decompression
Bottoms oil (hereinafter also referred to as " VR ") hydrodesulfurization and can make to these heavy hydrocarbon oil carry out hydrotreating and obtain
Hydrotreating oil storage-stable improve heavy hydrocarbon oil hydrotreating catalyst, the hydrotreating catalyst manufacture
Method and used the hydrotreating catalyst heavy hydrocarbon oil hydrotreating method.
The application is drawn herein based on the Patent 2013-201800 CLAIM OF PRIORITYs in Japanese publication on the 27th of September in 2013
With its content.
Background technology
Obtained from being handled as atmospheric distillation plant crude oil AR or by using vacuum distillation apparatus to AR into
In the heavy hydrocarbon oil such as VR obtained from the processing of one step, contain a large amount of sulphur compounds.By these heavy hydrocarbon oil without desulfurization process
And in the case of being used as fuel, a large amount of oxysulfide (SOx) discharged into air, become a reason of environmental disruption.
Therefore need to reduce the sulphur compound in heavy hydrocarbon oil.
It can be seen from the above, in order to reduce the sulphur compound in heavy hydrocarbon oil, the high activity in relation to hydrotreating catalyst,
The research of high life actively carries out.For example, the hydrotreating catalyst on alumina series, discloses：By in oxygen
To change in alumina supporter and contain zinc and phosphorus, the dispersity as the molybdenum of active metal becomes good, desulfurization performance raising (for example,
Referenced patent document 1).
On the other hand, on heavy hydrocarbon oil, the raising of storage-stable is expected.Heavy hydrocarbon oil after hydrotreating is in order to examine
Workability when considering during dispatching from the factory, dispatching from the factory and to keep mobility thus to carry out heating storage.In addition, product is made
After dispatching from the factory, long-term storage is wanted sometimes when use.Under atmosphere when therefore, according to thermal history and storage, storing sometimes
Period produces deposition, becomes filter occlusion, pumps the reason for breakage etc..
Several the main reason for producing deposition are enumerated, as one of them, can be included included in heavy hydrocarbon oil
Asphalitine component stability.Asphalitine component will not deposit by being enclosed in resin component but be distributed to heavy
In hydrocarbon ils.But departed from by hydrotreating, resin component, if the balance of asphalitine component and resin component is collapsed,
Then asphalitine component easily occurs in the form of deposition.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-290043 publications
The content of the invention
Problem to be solved by the invention
It is an object of the invention to provide the storage-stable that can improve the heavy hydrocarbon oil after hydrotreating to take off without making
Hydrotreating catalyst, the manufacture method of the hydrotreating catalyst and the use that sulphur activity and metal removal activity reduce should add
The method that hydrogen processing catalyst towards heavy matter hydrocarbon ils carries out hydrotreating.
The means used to solve the problem
The present inventors conduct in-depth research to achieve these goals, it turns out that：In the hydrogenation of heavy hydrocarbon oil
In processing, supported on the alumina support by using the phosphorous/zinc for the zinc oxide particles for making the particular size containing specified quantitative
Hydrotreating catalyst obtained from hydrogenation activity component, can be reduced the hydrotreating oil of potential deposition, so that
Complete the present invention.
That is, the hydrotreating catalyst of hydrotreating catalyst, heavy hydrocarbon oil the present invention relates to following heavy hydrocarbon oil
The hydrotreating method of manufacture method and heavy hydrocarbon oil.
[1] a kind of hydrotreating catalyst of heavy hydrocarbon oil, it is characterised in that using the aluminium oxide of phosphorous/zinc as carrier,
The alumina support of the phosphorous/zinc contains by the phosphorus of 0.1~4 mass % on the basis of carrier and based on oxide conversion and contains
There are the zinc oxide particles of based on the basis of carrier 1~12 mass %；Supported on above-mentioned carrier by the basis of catalyst and
8~20 mass % of oxide conversion meter selected from least one of the 6th race's metal of periodic table and by the basis of catalyst and
2~6 mass %'s of oxide conversion meter is selected from least one of the 8th~10 race's metal of periodic table；Wherein, above-mentioned oxidation zinc granule
The average grain diameter of son is 2~12 μm.
[2] a kind of manufacture method of the hydrotreating catalyst of heavy hydrocarbon oil, it is with following processes：
The process for preparing alumina gel；
Phosphorus compound and zinc compound are kneaded in above-mentioned alumina gel so that containing pressing on the basis of carrier and oxygen
The phosphorus of 0.1~4 mass % of compound conversion meter and the average grain diameter containing based on the basis of carrier 1~12 mass % are 2~12 μ
The process of the zinc oxide particles of m；
Obtained mixture is molded, it is dried, is burnt till, obtains the process of the alumina support of phosphorous/zinc；
And
Supported on the alumina support of above-mentioned phosphorous/zinc by 8~20 matter on the basis of catalyst and based on oxide conversion
That measures % is selected from least one of the 6th race's metal of periodic table and by 2~6 matter on the basis of catalyst and based on oxide conversion
Measure the process selected from least one of the 8th~10 race's metal of periodic table of %.
[3] a kind of hydrotreating method of heavy hydrocarbon oil, it is characterised in that at the hydrogenation of the heavy hydrocarbon oil of above-mentioned [1]
Manage catalyst in the presence of, hydrogen dividing potential drop be 3~20MPa, temperature is 300~420 DEG C, liquid hourly space velocity (LHSV) is 0.1~3h-1Under, into
The contact catalytic reaction of row heavy hydrocarbon oil.
Invention effect
The oxygen of phosphorous/zinc of zinc oxide particles of the hydrotreating catalyst of the present invention at the same time containing phosphorus and particular size
Change and be supported with hydrogenation activity component on alumina supporter, heavy hydrocarbon oil it is desulphurizing activated excellent.In addition, urged by using the hydrotreating
Agent carries out hydrotreating, can obtain being difficult to produce the excellent heavy hydrocarbon oil of deposition, storage-stable.
Embodiment
<Hydrotreating catalyst>
The hydrotreating catalyst of the present invention is used as carrier principal component using aluminium oxide.
As aluminium oxide, the various aluminium oxide such as Alpha-alumina, beta-alumina, gama-alumina, δ-aluminium oxide can be used,
The preferably aluminium oxide of Porous and high-specific surface area, wherein being especially advisable with gama-alumina.
In addition, the purity as the aluminium oxide of carrier principal component is preferably more than 98 mass %, more preferably 99 mass %
More than.
As the impurity in aluminium oxide, SO can be included4 2-、Cl-、Fe2O3、Na2O etc., preferably these impurity are as far as possible
It is few, it is preferably below 2 mass % in terms of total impurities, is more preferably below 1 mass %, the preferred SO in terms of each component4 2-For
Below 1.5 mass %, C1-、Fe2O3、Na2O is below 0.1 mass %.
Aluminium oxide for the carrier of the hydrotreating catalyst of the present invention can also make selected from zeolite, boron oxide, dioxy
One or more of SiClx and zirconium oxide Composite are made the alumina support after Composite.
In alumina support after the Composite, aluminium oxide is 92~99.9 mass %, is preferably 95~98 mass %, choosing
It is preferably 0~8 mass % from one or more of zeolite, boron oxide, silica and zirconium oxide.At this time, above-mentioned zeolite, oxygen
The Composite component of change boron, silica and zirconium oxide can usually use those of the carrier components as this kind of catalyst
Material.
Carrier for the hydrotreating catalyst of the present invention is in alumina support (including the carrying alumina after Composite
Body) in phosphorous/zinc also containing zinc and phosphorus alumina support.
Zinc and phosphorus are active in order to improve the desulphurizing activated and decarbonized slag of each active metal amount, as realizing active site
Matter raising component and add, play critically make high activity NiMoS phases, NiWS equal active metal-sulfur phases
Effect.
The content of zinc in the alumina support of above-mentioned phosphorous/zinc by the basis of carrier and oxide conversion be calculated as 1~
12 mass %, are preferably 2~9 mass %.In addition, by preferably 3~6 matter on the basis of catalyst and based on oxide conversion
Measure %.The content of zinc if more than 1 mass %, then can fully improve the 6th race's metal of periodic table based on the basis of carrier
Sulphidity.In addition, the content of zinc if below 12 mass %, is then difficult to the reduction for causing pore volume and specific surface area,
While the 6th race's metal of periodic table is fully dispersed, the sulphidity of the 8th~10 race's metal of periodic table is difficult to reduce.
In addition, in the present invention, " the 6th race's metal of periodic table " (following, sometimes referred to as " the 6th race's metal ") refers to long period type
The 6th race's metal in periodic table, " the 8th~10 race's metal of periodic table " (following, sometimes referred to as " the 8th~10 race's metal ") refer to grow
The 8th~10 race's metal in preiodic type periodic table.
In the hydrotreating catalyst of the present invention, the use of average grain diameter is 2~12 μm as zinc, be preferably 4~10 μm,
More preferably 5~9 μm of zinc oxide particles.The average grain diameter of the zinc oxide particles contained in carrier is if less than 12 μm, then
The interaction with aluminium oxide is fully obtained, can obtain having the heavy hydrocarbon after the hydrotreating of sufficient storage-stable
Oil.On the other hand, when the average grain diameter of the zinc oxide particles contained in carrier is more than 2 μm, in the alumina support of phosphorous/zinc
Manufacture when, zinc is easily mixed with aluminium oxide.
In addition, in the present invention and present specification, the particle diameter of zinc oxide particles passes through the laser based on JIS R1629
Diffraction scattering method is measured, using the volume of size distribution averagely as average grain diameter.In addition, the aluminium oxide as phosphorous/zinc
The zinc oxide particles contained in carrier, preferably purity are more than 99% particle.
The content of phosphorus in the carrier of the hydrotreating catalyst of the present invention is by the basis of carrier and based on oxide conversion
It is preferably 0.5~2.5 mass % for 0.1~4 mass %.In addition, the hydrotreating catalyst as the present invention, the content of phosphorus
By preferably 0.08~3.6 mass % on the basis of catalyst and based on oxide conversion.The content of phosphorus in carrier is pressed with carrier
On the basis of and oxide conversion when being calculated as more than 0.1 mass %, the sulphidity of the 6th race's metal fully improves.In addition, phosphorus contains
To measure if below 4 mass %, then will not cause the reduction of pore volume and specific surface area, the 6th race's metal fully disperses, because
This can obtain the additive effect of phosphorus.
The raw material compound of the phosphorus contained in carrier as the hydrotreating catalyst of the present invention, can use variousization
Compound.As phosphorus compound, can include such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphate, wherein, it is excellent
Elect orthophosphoric acid as.
In the present invention, on the content of zinc and phosphorus, " by the basis of carrier and based on oxide conversion " refers to：By carrier
Included in whole elements quality with the form calculus of each autoxidisable substance, the oxidation material of zinc for its gross mass
Ratio shared by the oxide mass of amount and phosphorus.The oxide mass of zinc be converted into zinc oxide, the oxide mass of phosphorus is
Phosphorus pentoxide is converted into try to achieve respectively.
It is thought that the addition of zinc and phosphorus into alumina support can relax the 6th race's metal of periodic table or periodic table the 8th~
The interaction of 10 race's metals and carrier, becomes easier to the vulcanization of the 6th race's metal and the 8th~10 race's metal.It is but another
Aspect, if the interaction of the 6th race's metal or the 8th~10 race's metal and carrier becomes too weak, causes the solidifying of active metal
It is poly-, it is therefore desirable to which that the addition to zinc and phosphorus carries out accurate control.In the hydrotreating catalyst of the present invention, it is believed that pass through essence
Thickly control addition zinc and phosphorus, while NiMoS phases, the state of NiWS equal active metal-sulfur phase high dispersives is kept, stacking
The structural forms such as number are also by optimization.
It is used for the alumina support of phosphorous/zinc of the hydrotreating catalyst of the present invention in order to obtain, first, passes through routine
Method prepares alumina gel.As long as material of the raw material of aluminium oxide comprising aluminium is just, arbitrary material can be used, but it is excellent
Elect the aluminium salts such as aluminum sulfate, aluminum nitrate as.These alumina raw materials are usually supplied in form of an aqueous solutions, its concentration is not special
Limit, be preferably 2~50 mass %, more preferably 5~40 mass %.
Aqueous sulfuric acid, sodium aluminate, aluminium hydroxide are mixed to make as the preparation of alumina gel, such as with stirred tank
Standby slurry.The moisture for carrying out being implemented using rotational circle cartridge type continuous vacuum filter to obtained slurry is removed, pure water cleaning,
Obtain alumina gel.Then, obtained alumina gel is cleaned until that cannot detect SO in filtrate4 2-And Na+, the alumina gel is suspended in pure water to obtain uniform slurry.By obtained alumina gel de-watering of slurries
Reach 60~90 mass % to amount of moisture, obtain filter cake.
In the manufacture method of the hydrotreating catalyst of the present invention, the alumina gel slurry is preferably carried out by filter press
Dehydration.It is dehydrated by using filter press, can improves the surface state of alumina support, to aftermentioned catalyst activity metal
The level of the sulphidity of (hydrogenation active metals) improves beneficial.In addition, preferably preparing oxygen using the dehydration procedure of the filter press
Carried out after changing at least one process in the process and the process of mixing phosphorus compound described later and zinc oxide particles of alumina gel,
It can also be carried out after any one process.More preferably after alumina gel is prepared, the mixing of phosphorus compound and zinc oxide particles
Preceding progress.
Here, filter press is to make compressed air or pump function in slurry come the filter that is filtered, also commonly referred to as
Pressure filter.There is plate-and-frame and notch board type in filter press.The filter plate of plate-and-frame pressure filter replaces with filter frame be fastened on end plate between, to
Slurry is pressed into filter frame to be filtered.Filter plate has the groove as filtrate stream, in stove frame upper berth stove cloth.On the other hand, it is recessed
The filter plate of filter cloth and notch board type is alternately arranged and is fastened between end plate by template pressure filter, forms filter chamber (bibliography：Change
Electrotechnics brief guide page 715).
In addition to this method, as the preparation method of alumina gel, it can include：Alumina raw material will be included
Method that aqueous solution is neutralized with neutralizers such as sodium aluminate, aluminic acid, ammonia, mix with precipitating reagents such as hexa, calcium carbonate
Method of conjunction etc..
The usage amount of neutralizer is not particularly limited, relative to the total of the aqueous solution comprising alumina raw material and neutralizer
Amount, is preferably 30~70 mass %.The usage amount of precipitating reagent is not particularly limited, relative to the aqueous solution comprising alumina raw material
It is preferably 30~70 mass % with the total amount of precipitating reagent.
As alumina support, in the case of the alumina support after the Composite components such as use zeolite and Composite,
First, alumina gel is prepared by a conventional method, obtained alumina gel is cured, is cleaned, is dehydrated, water
Point adjust, then, by coprecipitation, mixing method etc. by aluminium oxide and Composite component for compositeization.After Composite
Alumina gel is cured, cleaned, being dehydrated, moisture regulation.Before the shaping of alumina gel after Composite most
In whole dehydration procedure, it is also preferred that being dehydrated using filter press.
Then, phosphorus compound and zinc oxide particles are added by being kneaded in obtained alumina gel.It is specific and
Speech, it is water-soluble to be heated to 15~90 DEG C of phosphorus compound in the moisture regulation thing for be heated to 50~90 DEG C of alumina gel
Liquid and zinc oxide particles, are kneaded using heating kneader etc., are stirred, thus obtain phosphorous/zinc alumina support it is mixed
Refine thing.In addition, as set forth above, it is possible to alumina gel and phosphorus compound and zinc compound are being kneaded, profit is carried out after stirring
The dehydration implemented with filter press.
Then, obtained mixture is molded, it is dried, is burnt till, obtain the alumina support of phosphorous/zinc.
In the shaping of the mixture, can be carried out by the various forming methods such as extrusion molding, extrusion forming.
In addition, in the drying of obtained molding, drying temperature is preferably 15~150 DEG C, particularly preferably 80~
120 DEG C, drying time is preferably more than 30 minutes.In obtained dried object when burning till, firing temperature can be as needed
Appropriate setting, such as in order to form gama-alumina, preferably burnt till more than 450 DEG C, more preferably 480 DEG C~600
℃.More than when firing time is preferably 2 small, particularly preferably 3~12 it is small when.
The alumina support of phosphorous/zinc of the hydrotreating catalyst of the present invention preferably obtains following physics values.
The specific surface area of the alumina support of phosphorous/zinc is preferred in terms of the measured value obtained using nitrogen adsorption method (BET method)
For 200~380m2/ g, more preferably 220~360m2/g.When specific surface area is too small, the dispersiveness variation of hydrogenation active metals, takes off
Sulphur activity is likely to decrease；When specific surface area is excessive, pore diameter extremely diminishes, therefore the pore diameter of catalyst also diminishes,
During hydrotreating, diffusion of the sulphur compound into catalyst pore becomes inadequate, desulphurizing activated to be likely to decrease.By making to contain
The specific surface area of the alumina support of phosphorus/zinc within the above range, the favorable dispersibility of hydrogenation active metals, and can obtaining
The hydrotreating catalyst of pore diameter with abundant size.
Average pore diameter in the broad pore distribution measured by mercury penetration method of the alumina support of phosphorous/zinc is preferred
For 5~12nm, more preferably 6~10nm.By make phosphorous/zinc alumina support average pore diameter in above range
Interior, while with sufficient pore internal surface area, diffusivity of the reactive material in pore is also good, and desulphurization reaction is effective
Ground carries out, desulphurizing activated to further improve.
The pore volume of the alumina support of phosphorous/zinc is preferably 0.4 in terms of the measured value obtained using mercury penetration method
~0.9mL/g, more preferably 0.6~0.8mL/g.In the case where pore volume is too small, pass through (the impregnation of common method of impregnation
Method) when preparing catalyst, it is changed into a small amount of into the solvent in pore volume.Solvent is if a small amount of, then hydrogenation active metals
The dissolubility of compound is deteriorated, the dispersiveness reduction of metal, it is possible to form the catalyst of low activity.Although in the presence of in order to improve work
The dissolubility of property metallic compound and the method for largely adding the acid such as nitric acid, but if being excessively added, then cause the low table of carrier
Area, becomes the main reason of desulfurization performance reduction.On the other hand, in the case that pore volume is excessive, specific surface area extremely becomes
Small, the dispersiveness of active metal is likely to decrease.By make phosphorous/zinc alumina support pore volume in above range
It is interior, while with sufficient specific surface area, an adequate amount of solvent, therefore hydrogenation active metals are entered in pore volume
The dissolubility and dispersiveness of compound become good, desulphurizing activated to further improve.
On the alumina support of phosphorous/zinc, by comprising by 8~20 matter on the basis of catalyst and based on oxide conversion
Measure the choosing selected from least one of the 6th race's metal and by 2~5 mass % on the basis of catalyst and based on oxide conversion of %
Supported from the mode of at least one of the 8th~10 race's metal, the hydrotreating catalyst thus, it is possible to manufacture the present invention.
Here, the content on the 6th race's metal and the 8th~10 race's metal, " by the basis of catalyst and oxide changes
Calculate " refer to：With the quality of whole elements included in the form calculus catalyst of respective oxide, relative to total matter
Ratio for amount shared by the oxide mass of each metal.As the 6th race's metal and the oxidation material of the 8th~10 race's metal
Amount, is converted into the oxides of 6 valencys to try to achieve for the 6th race's metal, divalent is converted into for the 8th~10 race's metal
Oxide is tried to achieve.
As the 6th race's metal, molybdenum (Mo), tungsten (W), chromium (Cr) etc. can be included, wherein particularly preferred per unit mass
Active high Mo.As the Mo compounds supported on the alumina support of phosphorous/zinc, molybdenum trioxide, phosphorus can be included
Molybdic acid, ammonium molybdate, molybdic acid etc., are preferably phosphomolybdic acid, molybdenum trioxide, ammonium molybdate.
The content of the 6th race's metal in the alumina support of phosphorous/zinc is by the basis of catalyst and based on oxide conversion
It is preferably 10~16 mass % for 8~20 mass %.6th race's metal if more than 8 mass %, then can fully show by
Effect caused by 6th race's metal, if below 20 mass %, then the 6th race's metal is difficult to agglomerate, and the dispersiveness of active metal carries
It is high.That is, it will not occur significantly to drop more than the limit or catalyst surface area of effectively scattered active metallic content
It is low, so as to realize the raising of catalyst activity.
As the 8th~10 race's metal, nickel (Ni), cobalt (Co) etc. can be included, wherein particularly preferably hydrogenation can be high and urges
The low Ni of agent manufacturing cost.As the Ni compounds supported on the alumina support of phosphorous/zinc, the carbon of Ni can be included
Hydrochlorate, acetate, nitrate, sulfate, chloride, are preferably carbonate, acetate, more preferably carbonate.
The content of the 8th~10 race's metal in the alumina support of phosphorous/zinc is pressed on the basis of catalyst and oxide
Conversion is calculated as 2~6 mass %, is preferably 2.5~4.5 mass %.8th~10 race's metal is if more than 2 mass %, then fully
Ground obtains belonging to the active site of the 8th~10 race's metal.On the other hand, if below 6 mass %, then the 8th~10 race's metal
Compound is difficult to agglomerate, the dispersiveness raising of active metal.In the case where having used such as Ni, it is difficult to which generation is used as torpescence
The NiO kinds (as the presence of NiS kinds after catalyst vulcanization and in hydrotreating) of precursor and the intracell Ni points for entering carrier
Spar kind, therefore there is the raising of catalyst activity.
On the above-mentioned content of the 6th race's metal, each component of the 8th~10 race's metal, the 6th race as hydrogenation active metals
The optimum quality ratio of metal, the 8th~10 race's metal, with [the 8th~10 family metal oxide quality]/([the 8th~10 race's metal oxygen
Compound quality]+[the 6th family metal oxide quality]) value meter be preferably 0.14~0.3.
In the case of the 8th~10 race's metal phase is too small for the mass ratio of the total amount of the 6th race's metal and the 8th~10 race's metal
Under, it is believed that it is that the NiMoS phases of the active site of desulfurization, NiWS equal actives metal-sulfur mutually can not be generated fully, it is desulphurizing activated
It is possible without improving.In addition, in the case that the mass ratio is excessive, generation and active unrelated useless metal kind (NiS kinds,
Into the intracell Ni spinelles kind of carrier), catalyst activity is likely to decrease.By making above-mentioned mass ratio in above range
It is interior, active metal-sulphur phase is fully generated, and the generation of the useless metal kind unrelated with activity can be suppressed.
Can be leaching as the method for making the alumina support of phosphorous/zinc support the 6th race's metal and the 8th~10 race's metal
Ooze method known to method, coprecipitation etc..For example, as by the alumina support of phosphorous/zinc be impregnated into contain these hydrogenation live
Property metal ingredient solution in the state of make hydrogenation active metals such into the method for fractional precipitation, can also use make it is phosphorous/
The alumina support of zinc contacts with the solution containing hydrogenation active metals component, so that hydrogenation active metals be supported on it is phosphorous/
Method of impregnation on the alumina support of zinc.In addition, as infiltration the 6th race's metal and the 8th in the alumina support for making phosphorous/zinc
The method of~10 race's metal ingredients, can be one section of method of impregnation for making these each components while infiltration, or infiltrate respectively
Two sections of method of impregnation.
, can as making the 6th race's metal, the 8th~10 race's metal be supported on the specific method on the alumina support of phosphorous/zinc
To include the following method.First, prepare comprising the 6th race's metallic compound, the 8th~10 race's metallic compound, phosphorus compound
Infiltration solution.In addition, in the case of containing phosphorus in metallic compound, phosphorus compound, or addition appropriate amount are added without
Phosphorus compound.During preparation, in order to promote the dissolving of these compounds, can also be heated (30~100 DEG C), acid (nitric acid,
Phosphoric acid, organic acid (citric acid, acetic acid, malic acid, tartaric acid etc.)) addition.
Here, the mass ratio in terms of oxide conversion for the phosphorus being kneaded in the carrier for the 6th race's metal, preferably
For less than 0.25.If less than 0.25, then the surface area of catalyst and pore volume will not be reduced, and can not only suppress to be catalyzed
The reduction of agent activity, and acid amount will not increase, can anti-blocking separate out, thus inhibitory activity deteriorates.
Then, the infiltration of preparation is slowly added with solution and be infiltrated up in the alumina support of phosphorous/zinc so that it is reached
To uniform.Infiltrate the time when being preferably 1 minute~5 small, more preferably 5 minutes~3 it is small when, temperature is preferably 5~100 DEG C, more
Preferably 10~80 DEG C, atmosphere is not particularly limited, and is suitably in air, in nitrogen, in vacuum respectively.
After infiltration supports the 6th race's metal and the 8th~10 race's metal ingredient, in general, in nitrogen stream, in air draught
Or in vacuum, at room temperature~80 DEG C, by moisture, (LOI (loss on ignition, Loss on ignition) reaches to a certain extent
Less than 50%) remove, with drying oven in air draught, when drying 10 minutes~10 is small at 80~150 DEG C.Then, with burning till
Stove in air draught, carried out preferably at 300~700 DEG C, more preferably at 500~650 DEG C preferably 10 minutes~10 it is small when,
More preferably 3 it is small when more than burn till.
It is excellent in order to improve the hydrogenation activity for heavy hydrocarbon oil, desulphurizing activated for the hydrotreating catalyst of the present invention
Choosing adjusts its specific surface area, pore volume, average pore diameter and broad pore distribution to following scope.
The specific surface area of the hydrotreating catalyst of the present invention in terms of the measured value obtained using BET method preferably 180~
320m2/ g, more preferably 200~300m2/g.When specific surface area is too small, the dispersiveness variation of hydrogenation active metals, specific surface area
When excessive, pore diameter extremely diminishes, therefore the pore diameter of catalyst also diminishes.By the hydrorefining catalyst for making the present invention
The specific surface area of agent within the above range, can make the dispersiveness of hydrogenation active metals and during hydrotreating sulphur compound to catalysis
Both diffusivitys in agent pore become better.
The present invention hydrotreating catalyst pore volume in terms of the measured value obtained using mercury penetration method be preferably
0.45~0.8mL/g, more preferably 0.5~0.7mL/g.In the case where pore volume is too small, in hydrotreating, vulcanization is closed
Thing being diffused with catalyst pore may become inadequate；In the case where pore volume is excessive, specific surface area is possible to
Extremely diminish.Pore volume by making hydrotreating catalyst of the invention within the above range, can make hydrogenation activity golden
Both diffusivity of the sulphur compound into catalyst pore become better when the dispersiveness of category and hydrotreating.
Average pore diameter in the broad pore distribution measured by mercury penetration method of the hydrotreating catalyst of the present invention
Preferably 7~13nm, more preferably 7~12nm.By making the average pore diameter of hydrotreating catalyst of the invention upper
In the range of stating, while with sufficient pore internal surface area (that is, the effective ratio area of catalyst), reactive material is thin
Diffusivity in hole is also good, can make desulphurizing activated further improve.
In addition, in order to increase the significant figure for the pore for meeting above-mentioned pore condition, the hydrorefining catalyst as the present invention
The broad pore distribution of agent, the total measurement (volume) of the pore of the pore diameter with average pore diameter ± 1.5nm is relative to total pore volume
Ratio be preferably more than 45%, more preferably more than 55%.
In addition, the distribution as the hydrogenation active metals in the hydrotreating catalyst of the present invention, preferably exists
The homogeneous type that active metal is evenly distributed in catalyst.
<Hydrotreating method>
The hydrotreating method of the present invention is following method：It is 3~20MPa, is preferably 8~19MPa, temperature in hydrogen dividing potential drop
For 300~420 DEG C, be preferably 350~410 DEG C and LHSV (liquid hourly space velocity (LHSV)) be 0.1~3h-1, be preferably 0.15~2h-1's
Under the conditions of, the hydrotreating catalyst of the present invention is contacted with feedstock oil, progress hydrotreating, reduce sulphur in the feedstock oil into
Point.
Temperature then can fully play catalyst activity, particularly metal removal activity if more than 300 DEG C.It is another
Aspect, if less than 420 DEG C, then the thermal cracking of heavy hydrocarbon oil moderately carries out, it is difficult to causes catalyst degradation.
Hydrogen dividing potential drop is easily carried out if more than 8MPa, then hydrogenation reaction, if below 20MPa, then can be fitted
The metal removal activity of degree, therefore catalyst life.
As the heavy hydrocarbon oil of the hydrotreating method for the present invention, can include：Obtained from crude oil by distillation
Air-distillation residue oil, vacuum distillation residue oil, as thermal cracking oil visbreaking oil, as the heavy hydrocarbon beyond oil
Asphalt sand oil, shale oil etc. or their mixture of oil etc., be preferably air-distillation residue oil, vacuum distillation residue oil,
Or their miscella.
In the case where air-distillation residue oil is mixed with vacuum distillation residue oil, as mixed proportion, although also root
According to its character difference, different but usually used situations is in a manner of being evaporated under reduced pressure residue oil and reach about 1~60 capacity %
Mixed.
As the heavy hydrocarbon oil of the hydrotreating method for the present invention, preferred density is 0.91~1.10g/cm3, especially
It is 0.95~1.05g/cm3, sulphur component be 2~6 mass %, the particularly metal ingredient such as 2~5 mass %, nickel, vanadium be 1~
1500ppm, particularly 20~400ppm, asphalitine component are 2~15 mass %, are particularly the heavy hydrocarbon oil of 3~10 mass %.
The present invention hydrotreating method in other hydroprocessing conditions can according to required extent of reaction etc. come
It is appropriate selected.For example, hydrogen/oil is than being preferably 400~3000m3/m3, more preferably 500~1800m3/m3。
The hydrotreating catalyst of the present invention usually before use the hydrotreating method of the present invention (that is, carry out before),
Vulcanizing treatment is carried out in reaction unit to activate.The vulcanizing treatment usually 200~400 DEG C, be preferably 250~350 DEG C, often
Under the nitrogen atmosphere of pressure or the hydrogen dividing potential drop more than it, using the petroleum distillate comprising sulphur compound, in the petroleum distillate
Material or hydrogen sulfide obtained from adding the vulcanizing agent such as dimethyl disulphide or carbon disulfide carry out.
In the case where carrying out the hydrotreating method of the present invention with commercial size, this hair can be formed in reaction unit
The catalyst layer of bright hydrotreating catalyst, imports feedstock oil in the reaction unit, carries out being hydrogenated with these conditions anti-
Should.
The catalyst layer can be any one in fixed bed, moving bed or fluidized bed type.In the case of most commonly, it is
Following method：Fixed-bed type catalyst layer is formed in reaction unit, feedstock oil is imported the top of reaction unit, from top to bottom
By fixed bed, make the method that product flows out from the lower part of reaction unit；Or feedstock oil is conversely set to import reaction unit
Lower part, from top to bottom by fixed bed, makes the method that product flows out from the top of reaction unit.
The hydrotreating method of the present invention can be that the hydrotreating catalyst of the present invention is filled into individually reaction dress
The one-stage hydrogenation processing method for putting to carry out or the multistage continuously hydrogen adding for being filled into several reaction units to carry out
Processing method.
Embodiment
Then, embodiments of the present invention and its effect are explained in more detail by embodiment etc., but this hair
Bright any restriction from these examples.
The average grain diameter of zinc oxide particles used in embodiment and comparative example is shown in table 1.In addition, oxidation zinc granule
The particle diameter of son is measured by the laser diffraction scattering method based on JIS R1629, using the volume of size distribution averagely as flat
Equal particle diameter.
Table 1
| Average grain diameter (μm) | |
| Zinc oxide 1 | 5.5 |
| Zinc oxide 2 | 7.1 |
| Zinc oxide 3 | 0.5 |
| Zinc oxide 4 | 15.0 |
The preparation of [embodiment 1] hydrotreating catalyst A
First, the preparation of the alumina support of phosphorous/zinc is carried out.The aqueous sulfuric acid 1.5L of 12 mass % is put into and is filled
Enter in the pure water 100L in stirred tank, after being heated to 95 DEG C, be vigorously stirred after five minutes with agitating paddle, thrown in the stirred tank
Enter alumina concentration be 70g/L sodium aluminate 3.9L, thus prepare aluminium hydroxide, with stirring paddle stirring 24 it is small when.By obtained by
Slurry put into filter, filtered, remove moisture after, by obtained gel using pure water cleaned until filter
It can't detect SO in liquid4 2-、Na+.Then, the gel after cleaning is suspended in pure water, uniform slurry is made, by the slurry
Put into pressure filter.The slurry is deposited on filter plate across filter cloth, is dehydrated by Filter pressing board.
Filtering is interrupted at the time of amount of moisture in obtained filter cake reaches 80%.Filter cake input hot type is mediated
In machine (design temperature is 80 DEG C), fully it is kneaded to reach uniformly, then, puts into phosphoric acid and as oxidation zinc granule
The zinc oxide 1 of son, is further kneaded to reach uniformly.Obtained filter cake is put into after being kneaded and is extruded into
In type device, the extrusion molding thing for the four blade profile shapes that major diameter is 1.3mm, minor axis is 1.1mm is obtained.The molding is dried, is connect
Burnt till at 600 DEG C 4 it is small when, thus obtain the alumina support of phosphorous/zinc.The alumina support of obtained phosphorous/zinc
Containing by the phosphorus of 1.2 mass % on the basis of carrier and based on oxide conversion and by the basis of carrier and based on oxide conversion
The zinc of 4.0 mass %, pore volume 0.73mL/g, specific surface area 307m2/ g, average pore diameter 7.7nm.
Alumina support (γ-the Al of above-mentioned phosphorous/zinc are put into eggplant type flask2O3Matrix, diameter 1.33mm ×
The four blade profile moldings of 1.10mm) 50.00g.It will be dissolved in ion exchange water 37.6g molten obtained from ammonium molybdate 8.76g
Drop be added in the alumina support of above-mentioned phosphorous/zinc after standing, then, make its dry after, burnt till at 500 DEG C 4 it is small when, by
This obtains supporting the alumina support of phosphorous/zinc of molybdenum.Then, dripped on the alumina support of the above-mentioned phosphorous/zinc for supporting molybdenum
Stood after being added in solution obtained from having dissolved nickel nitrate 9.27g in ion exchange water 31.8g, then, after drying it,
Burnt till at 650 DEG C 4 it is small when, thus obtain catalyst A.
The preparation of [embodiment 2] hydrotreating catalyst B
In addition to zinc oxide 1 is replaced with zinc oxide 2, operate similarly to Example 1 to prepare hydrorefining catalyst
Agent B.
The preparation of [comparative example 1] hydrotreating catalyst a
In addition to zinc oxide 1 is replaced with zinc oxide 3, operate similarly to Example 1 to prepare hydrorefining catalyst
Agent a.
The preparation of [comparative example 2] hydrotreating catalyst b
In addition to zinc oxide 1 is replaced with zinc oxide 4, operate similarly to Example 1 to prepare hydrorefining catalyst
Agent b.
<The physical behavior and chemical property of carrier and catalyst>
By the character of the carrier of hydrotreating catalyst A, B, a and b for being prepared in embodiment 1,2 and comparative example 1,2
[content of phosphorus and zinc (by the basis of carrier and based on oxide conversion), average pore diameter, specific surface area and pore hold
Product] it is shown in table 2.
By the character of hydrotreating catalyst A, B, a and b for being prepared in embodiment 1,2 and comparative example 1,2 [Mo and
Loading (by the basis of catalyst and based on oxide conversion), the loading of phosphorus and zinc of Ni (is pressed on the basis of catalyst
And oxide conversion meter), average pore diameter, specific surface area, pore volume and broad pore distribution] be shown in table 3.
In table 3, " Ni/Mo (epimere) 4/12 (hypomere) " in " active metal _ active metal amount (quality %) " item refers to：
The catalyst contains the Mo by the Ni and 12 mass % of 4 mass % on the basis of catalyst and based on oxide conversion.
In addition, in table 3, " broad pore distribution " refers to the total of the pore with the pore diameter of average pore diameter ± 1.5nm
Volume relative to total pore volume ratio.In addition, the physical behavior and chemical property of catalyst will get survey by following
It is fixed.
[1] analysis (specific surface area, pore volume, average pore diameter and broad pore distribution) a of physical behavior) measure side
Method and use equipment：
Specific surface area is measured by using the BET method that N2 adsorption is implemented.N2 adsorption device uses BEL plants of formula meetings of Japan
The surface area determination unit (BELSORP Mini) of society's manufacture.
Pore volume, average pore diameter and broad pore distribution are measured by mercury penetration method.Mercury press-in device makes
With porosimeter (MICROMERITICS AUTO-PORE 9200：Shimadzu Seisakusho Ltd.'s system).
B) measuring principle：
Law of the mercury penetration method based on capillarity.In the case of mercury and cylinder pore, which passes through
Following formula represents.In formula, D is pore diameter, P is the pressure of application, γ is surface tension, θ is contact angle.
Measure is as the function of the pressure P of application into the mercury volume in pore.In addition, the pore mercury of catalyst
Surface tension be set to 484 dynes per centimeters, contact angle is set to 130 degree.
Formula：4 γ cos θ of D=- (1/P)
Pore volume is total mercury volume relative to every gram of catalyst for entering pore.Average pore diameter is work
The average value of the D calculated for the function of P.
Broad pore distribution is using the distribution of the P D calculated as function.
C) determination step：
1) open heating in vacuum degasser power supply, confirmation reach temperature be 400 DEG C, vacuum be 5 × 10-2Support with
Under.
2) sample buret is installed on heating in vacuum degasser with empty state.
3) vacuum one reaches 5 × 10-2Support is following, is shut off its cock and the sample buret deaerates from heating in vacuum
Unloaded on device, after cooling, measure weight.
4) sample (carrier or catalyst) is loaded in the sample buret.
5) the sample buret with sample is installed on heating in vacuum degasser, vacuum reaches 5 × 10-2Support is following
Afterwards, more than when holding 1 is small.
6) the sample buret with sample is unloaded from heating in vacuum degasser, after cooling, measures weight, obtain examination
Sample weight.
7) sample is fitted into AUTO-PORE 9200 with trough pool.
8) it is measured by AUTO-PORE 9200.
[2] analysis of chemical composition
A) analysis method and equipment is used：
The metal analysis of carrier and catalyst uses inductively coupled plasma luminesceence analysis (ICPS-2000：Shimadzu
Make made) carry out.
Metal is quantitatively carried out by absolute standard curve method.
B) determination step：
1) sample 0.05g, hydrochloric acid (50 mass %) 1mL are put into single hole groove, hydrofluoric acid one drips and pure water 1mL, add
Heat makes its dissolving.
2) after dissolving, obtained solution is transferred in polypropylene measuring bottle (50mL volumes), adds pure water, is quantified extremely
50mL。
3) solution is measured by ICPS-2000.
Table 2
Table 3
<The hydrotreating reaction of heavy hydrocarbon oil>
The hydrotreating of the air-distillation residue oil (AR) of following characters is carried out by following main points.Urged as hydrotreating
Agent, respectively using catalyst A, B, a and the b manufactured in embodiment 1,2, comparative example 1,2.
First, hydrotreating catalyst is filled into high pressure flow type reaction unit, forms fixed-bed type catalyst layer,
Pre-treatment is carried out under the following conditions.Then, the feedstock oil of reaction temperature and the mixed flow of the gas containing hydrogen be will warm up
Body is imported by the top of the reaction unit, is carried out desulphurization reaction and the hydrogenation reaction as cracking reaction under the following conditions, is made
Generation oil and the fluid-mixing of gas are flowed out by the lower part of the reaction unit, and oil is generated by gas-liquid separator separates.
On assay method, density is based on JIS K 2249-1 " crude oil and petroleum product-density test method and close
Spend quality capacity conversion table (oscillatory type density test method) ", sulphur component is based on JIS K 2541-4 " crude oil and oil
Product-sulphur component testing method the 4th：Radiate wire type excitation method ", potential deposition component is based on JPI-5S-60-2000.Specifically
For, potential deposition content is analyzed by the following method.
<The determination step of potential deposition content>
1) take the sample 25g for being heated to 60 DEG C to add into conical flask, aerial condenser is installed, is inserted into 100 DEG C
In oil bath, when holding 24 is small.
2) by after the sample shake well, 10.5g is into glass beaker for sampling.
3) glass beaker equipped with sample is heated 10 minutes at 100 DEG C.
4) dried glass fiber filter paper (a diameter of 47mm, hole diameter are 1.6 μm) is overlapped with 3,
It is decompressed to drawdown pump in the vacuum filter of 80kPa and puts into said sample, 40kPa is decompressed to after 30 seconds.
5) filtering terminates, after its surface drying, further continual reduction in pressure 5 minutes.
6) after drawdown pump stops, while with asepwirator pump suction strainer, with cleaning solvent (the heptane 85mL+ of 25mL
Toluene 15mL) clean funnel and all parts of filter.
7) further with the filter paper (from upper number the 1st) for after the 20mL washed with heptane filter paper, removing topmost, with 20mL heptan
Alkane cleans the filter paper of lower part.
8) by from the filter paper of upper number the 1st and the 2nd at 110 DEG C it is dry after twenty minutes, natural cooling 30 minutes.
9) the 1st after measure filtering and the 2nd filter paper are relative to the respective weight gain before filtering, by the 1st filter
The increase weight of paper subtracts the weight obtained after the increase weight of the 2nd filter paper relative to the percentage of sampling weight as potential
Deposit (quality %).
In addition, filtering in the case where 25 minutes are not over, makes sample size be measured again for 5g or 2g.
The content of nickel and vanadium is based on institute of Petroleum's standard JPI-5S-62-2000 " petroleum product metal analysis test method(s)s
(ICP luminescence analysis) ".
Asphalitine component is after adding toluene in the sample, to be filtered with cellulose filter, recycles toluene insoluble solution component.
Using the insoluble composition as asphalitine component.
Resin component is after adding toluene in the sample, to be filtered with cellulose filter, is dissolved as the toluene of filtrate
Component concentrates.N-heptane solution obtained from adding heptane in the concentrate is set to circulate in activated alumina chromatography column,
Saturation, aromatic series, resin component are separated into, recycles resin component.
The Pretreatment of catalyst：
The presulfurization of catalyst be by depressurize light oil hydrogen dividing potential drop carry out for 10.3MPa, at 370 DEG C 12 it is small when.Then,
It is replaced with the feedstock oil of activity rating.
Reaction condition：
Reaction temperature；385℃、
Pressure (hydrogen dividing potential drop)；10.3MPa、
Liquid hourly space velocity (LHSV)；0.4h-1、
Hydrogen/oil ratio；1690m3/m3。
The character of feedstock oil：
Oil kind；The air-distillation residue oil of Middle East system crude oil,
Density (15 DEG C)；0.9759g/cm3、
Sulphur component；3.51 mass %,
Vanadium；59ppm、
Nickel；11ppm、
Asphalitine component；2.8 mass %.
On catalyst activity, analyzed by the following method.Reaction unit is operated at 385 DEG C, gathers operation start
Generation oil after 25 days, analyzes its character (desulfurization degree (HDS) (%), desulphurization reaction velocity constant (Ks), desulfurization specific activity
(%), demetallization per (HDM)).Show the result in table 4.
[1] desulfurization degree (HDS) (%)：Sulphur component in feedstock oil is converted into hydrogen sulfide by desulphurization reaction, thus will
The ratio of the sulphur component to disappear from feedstock oil is defined as desulfurization degree, by following formula (1) by feedstock oil and the sulphur of generation oil
Assay value calculates.
[2] desulphurization reaction velocity constant (Ks)：Relative to the decrement of the sulphur component (Sp) of generation oil, 2 times will be obtained instead
The constant of the rate cquation of number is answered as desulphurization reaction velocity constant (Ks).Calculated by following formula (2).In addition,
Rate constant is higher, represents that catalyst activity is more excellent.
[3] desulfurization specific activity (%)：Represented with the relative value when desulphurization reaction velocity constant of catalyst A is set to 100.
Calculated by following formula (3).
[4] demetallization per (HDM) (%)：By the ratio of the metal ingredient to disappear from feedstock oil (total amount of nickel and vanadium)
Demetallization per is defined as, is calculated by the metal analysis value of feedstock oil and generation oil by following formula (4).
Desulfurization degree (%)=[(Sf-Sp)/Sf] × 100 (1)
Desulphurization reaction velocity constant=[1/Sp-1/Sf] × (LHSV) (2)
In formula, Sf：Sulphur component (quality %) in feedstock oil,
Sp：Generation oil in sulphur component (quality %),
LHSV：Liquid hourly space velocity (LHSV) (h-1)。
Desulfurization specific activity (%)=(the desulphurization reaction speed of desulphurization reaction velocity constant/catalyst A of each catalyst is normal
Number) × 100 (3)
Demetallization per (%)=[(Mf-Mp)/Mf] × 100 (4)
In formula, Mf：The total amount (quality ppm) of nickel and vanadium in feedstock oil,
Mp：The total amount (quality ppm) of nickel and vanadium in generation oil.
[analysis of generation oil]
The desulfurization that the generation oil for being the 25th day by the days of operation obtained by above-mentioned hydrotreating reaction is obtained is than living
Property, demetallization per, resin component, asphalitine component, asphalitine component relative to resin component content ratio (mass ratio, [pitch
Matter component (quality %)]/[resin component (quality %)]) and it is potential deposition content the results are shown in table 4.
Table 4
| Embodiment | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| The species of catalyst | Catalyst A | Catalyst B | Catalyst a | Catalyst b |
| Desulfurization specific activity (catalyst A=100) | 100 | 99 | 97 | 99 |
| Demetallization per (%) | 73 | 74 | 75 | 75 |
| Resin component (quality %) | 3.6 | 3.7 | 3.1 | 3.2 |
| Asphalitine component (quality %) | 2.0 | 2.0 | 1.9 | 2.0 |
| Asphalitine component/resin component (mass ratio) | 0.56 | 0.54 | 0.61 | 0.63 |
| Potential deposition (quality %) | 0.5 | 0.5 | 0.9 | 1.0 |
As a result, the desulfurization specific activity and demetallization per of any catalyst are nearly all same degrees.On the other hand, on life
Into the resin component in oil and potential deposition, using the situation of catalyst A or catalyst B with using catalyst a or catalyst b
Situation compare, resin component is more, and potential deposition is substantially few.That is, the life obtained using catalyst A or catalyst B
The generation oil phase ratio obtained into oil and using catalyst a or catalyst b, it is difficult to produce deposition, storage-stable is excellent.
As knowen from these results, by using the size of the zinc oxide particles contained in the alumina support for making phosphorous/zinc
Hydrotreating catalyst in particular range, can reduce the content of the potential deposition in the heavy hydrocarbon oil after hydrotreating,
Storage-stable can be improved, without reducing the desulphurizing activated of hydrotreating catalyst.
Industrial applicability
The storage-stable that the present invention can provide the heavy hydrocarbon oil after can improving hydrotreating is desulphurizing activated without making
With metal removal activity reduce hydrotreating catalyst, the hydrotreating catalyst manufacture method and use the hydrotreating
The method that catalyst towards heavy matter hydrocarbon ils carries out hydrotreating.
Claims (3)
1. a kind of hydrotreating catalyst of heavy hydrocarbon oil, it is characterised in that using the aluminium oxide of phosphorous/zinc as carrier, this contains
The alumina support of phosphorus/zinc contain by the basis of carrier and oxide conversion based on 0.1~4 mass % phosphorus and containing by
The zinc oxide particles of 1~12 mass % are counted on the basis of carrier；
Support on the carrier by 8~20 mass % are selected from periodic table the 6th on the basis of catalyst and based on oxide conversion
At least one of race's metal and by the basis of catalyst and oxide conversion based on 2~6 mass % selected from periodic table the 8th~
At least one of 10 race's metals；
Wherein, the average grain diameter of the zinc oxide particles is 2~12 μm, and the average grain diameter is by based on JIS R1629
The volume for the size distribution that laser diffraction scattering method is measured is averaged.
2. a kind of manufacture method of the hydrotreating catalyst of heavy hydrocarbon oil, it is with following processes：
The process for preparing alumina gel；
Phosphorus compound and zinc compound are kneaded in the alumina gel so that containing pressing on the basis of carrier and oxide
It is 2~12 μm that the phosphorus of 0.1~4 mass % and the average grain diameter containing based on the basis of carrier 1~12 mass % are counted in conversion
Zinc oxide particles process；
Obtained mixture is molded, it is dried, is burnt till, obtains the process of the alumina support of phosphorous/zinc；And
Supported on the alumina support of the phosphorous/zinc by 8~20 mass % on the basis of catalyst and based on oxide conversion
Selected from least one of the 6th race's metal of periodic table and by 2~6 mass % on the basis of catalyst and based on oxide conversion
Process selected from least one of the 8th~10 race's metal of periodic table,
Wherein, the average grain diameter is the size distribution being measured by the laser diffraction scattering method based on JIS R1629
Volume is averaged.
3. a kind of hydrotreating method of heavy hydrocarbon oil, it is characterised in that at the hydrogenation of the heavy hydrocarbon oil described in claim 1
Manage catalyst in the presence of, hydrogen dividing potential drop be 3~20MPa, 300~420 DEG C, liquid hourly space velocity (LHSV) be 0.1~3h-1Under, carry out heavy
The contact catalytic reaction of hydrocarbon ils.
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| GB201615209D0 (en) | 2016-09-07 | 2016-10-19 | Mexichem Fluor Sa De Cv | Catalyst and process using the catalyst |
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| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US10655074B2 (en) | 2017-02-12 | 2020-05-19 | Mag{hacek over (e)}m{hacek over (a)} Technology LLC | Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| JP6916021B2 (en) * | 2017-03-30 | 2021-08-11 | Ｅｎｅｏｓ株式会社 | Method for producing hydrodesulfurization catalyst of hydrocarbon oil and hydrodesulfurization catalyst |
| WO2021193617A1 (en) * | 2020-03-26 | 2021-09-30 | コスモ石油株式会社 | Hydroprocessing catalyst for heavy hydrocarbon oil, method for producing hydroprocessing catalyst for heavy hydrocarbon oil, and method for hydroprocessing heavy hydrocarbon oil |
| US20230295522A1 (en) * | 2020-07-03 | 2023-09-21 | Cosmo Oil Co., Ltd. | Hydrotreating catalyst for hydrocarbon oil, method for producing hydrotreating catalyst for hydrocarbon oil, and method for hydrocarbon oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686374A (en) * | 1994-09-01 | 1997-11-11 | Japan Energy Corporation | Catalyst for hydroprocessing |
| JP2008290043A (en) * | 2007-05-28 | 2008-12-04 | Cosmo Oil Co Ltd | Hydrotreatment catalyst for heavy hydrocarbon oil, method for producing same, and hydrotreatment method |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3904550A (en) * | 1973-10-19 | 1975-09-09 | Exxon Research Engineering Co | Hydrocarbon conversion catalyst comprising alumina and aluminum phosphate |
| US4652546A (en) | 1984-08-27 | 1987-03-24 | Phillips Petroleum Company | Hydrogel derived catalyst of zinc titanate and alumina promoted with cobalt and molybdenum for hydrodesulfurization or hydrodenitrogenation |
| US6013598A (en) * | 1996-02-02 | 2000-01-11 | Exxon Research And Engineering Co. | Selective hydrodesulfurization catalyst |
| JPH09248460A (en) * | 1996-03-14 | 1997-09-22 | Japan Energy Corp | Catalyst for hydrogenating treatment of heavy oil and hydrogenating treatment method |
| US6716525B1 (en) * | 1998-11-06 | 2004-04-06 | Tapesh Yadav | Nano-dispersed catalysts particles |
| JP4638610B2 (en) | 2001-01-05 | 2011-02-23 | 日本ケッチェン株式会社 | Hydrotreating catalyst and hydrotreating method |
| JP4519379B2 (en) | 2001-09-28 | 2010-08-04 | 財団法人石油産業活性化センター | Heavy hydrocarbon oil hydrotreating catalyst |
| JP2005314657A (en) | 2004-03-29 | 2005-11-10 | Cosmo Oil Co Ltd | Method for hydrotreating heavy hydrocarbon oil |
| DE102005004429A1 (en) | 2005-01-31 | 2006-08-10 | Süd-Chemie AG | Process for the preparation of a catalyst for the desulfurization of hydrocarbon streams |
| JP5439673B2 (en) * | 2009-03-23 | 2014-03-12 | 一般財団法人石油エネルギー技術センター | Method for hydrotreating heavy hydrocarbon oil |
| CN101954282A (en) | 2010-08-31 | 2011-01-26 | 内江天科化工有限责任公司 | Hydrodesulphurization catalyst and preparation method thereof |
| CN103320159B (en) | 2013-06-24 | 2015-08-12 | 大连理工大学 | A kind of method removing mercaptan sulfur in catalytically cracked gasoline |
| EP3050622B1 (en) * | 2013-09-27 | 2021-05-05 | Cosmo Oil Co., Ltd. | Hydrogenation catalyst for heavy hydrocarbon oil and hydrogenation method for heavy hydrocarbon oil |
| KR102192541B1 (en) * | 2013-09-27 | 2020-12-17 | 코스모세키유 가부시키가이샤 | Hydrogenation treatment catalyst for heavy hydrocarbon oil, and method for hydrogenation treatment of heavy hydrocarbon oil |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686374A (en) * | 1994-09-01 | 1997-11-11 | Japan Energy Corporation | Catalyst for hydroprocessing |
| JP2008290043A (en) * | 2007-05-28 | 2008-12-04 | Cosmo Oil Co Ltd | Hydrotreatment catalyst for heavy hydrocarbon oil, method for producing same, and hydrotreatment method |
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